JPS58134636A - Image stabilizing solution for processing silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To prevent stains in an unexposed part during storage, and fading of image dyes, by adding a water-soluble bismuth compd. together with a specified aq. chelating agent soln. to an image stabilizing soln. after developing, bleaching, and fixing treatments. CONSTITUTION:A water-soluble bismuth compd., especially a bismuch complex formed from a bismuth compd. and a metal ion chelating agent is highly soluble in water and effective. A water-soluble chelating agent especially having stability constant (-log KMA) of >=3 as shown in the equation in which M is a bismuth ion, and A is a complex-forming anion, such as diethylenetriaminepentaacetate or condensed phosphoric acid is contained in an image stabilizing soln. used for a silver halide photosensitive material.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an image stabilizing solution used in the processing of silver halide photographic light-sensitive materials, and more particularly relates to an image stabilizing solution that prevents the occurrence of contamination due to storage of unexposed areas after processing. Regarding stabilizing liquid.

Generally, in silver halide color photographic materials, after image exposure, a dye image is formed through a series of photographic processes whose basic steps are a color development step and a desilvering step, and at the same time reduced silver is produced. The silver produced here is oxidized by the whitening agent, transformed into a soluble silver complex by the action of the fixing agent, and dissolved and removed by washing with water. Then, by performing water washing and image stabilization treatment, the silver complex salt is removed and the dye image is stabilized. The dye images obtained through this series of processing will fade due to long-term storage, and the unexposed white areas will be contaminated with a yellowish brown color (hereinafter referred to as yellow stain), which can be a hindrance to photographic appreciation. becomes. In particular, when preservation is performed under strong light illumination, high temperature, and high humidity, fading of the dye and increase in yellow stain occur strongly, but yellow stain occurs in a short period of time, especially under such conditions. It is known to occur frequently and cause major problems. Therefore, the yellow color that occurs in a short period of time when preserving color photographs is
It is strongly desired to prevent the occurrence of stains.

Conventionally, various techniques have been known for preventing yellow stain in colored images produced by silver halide color photographic materials. For example, U.S. Patent No. 2.788.274, U.S. Pat.
No. 369, No. 49-20537, Japanese Patent Application Laid-open No. 1973-
No. 47341, No. 48-90526, No. 49-834
Water-soluble aluminum salts, water-soluble zinc salts, water-soluble zirconium salts, sulfites, borates, mono-, di-, or polycarboxylic acids, water-soluble aldehyde compounds, and water-soluble methylol compounds described in each publication No. 41 are used alone or There is a technology for processing with image stabilizing liquid, so-called stabilizing liquid, which uses these in combination.
Treatment with a liquid containing an ultraviolet absorber described in each publication No. 975,
, as seen in the technology and Japanese Patent Publication No. 48-30495□
As shown in FIG. However, these methods have the disadvantage that only a small effect can be obtained, and even if yellow stain can be prevented, fading of the image dye is accelerated.

In recent years, environmental conservation and water resource protection have become important issues in photofinishers, which automatically and continuously develop color photographic materials. It is desired to reduce the amount of washing water that is used for toilet purposes in the subsequent washing process. but,
When simply reducing the washing water, an organic acid ferric complex salt (generally, an organic acid ferric complex salt is used as a silver bleaching agent).

) has the disadvantage that, especially if the water washing treatment is insufficient, the increase in yellow stain due to long-term storage of the processed dye image is accelerated. or,
If the amount of washing water mentioned above is simply reduced, thiol, which is commonly used as a fixing agent, sulfates, thiostones, and acid silver complexes will be mixed into the washing water.□
,,.

Therefore, not only does the amount of contamination increase over time, resulting in the generation of silver sulfide, but also the contaminated washing water gets mixed into the stabilizing solution that is often used in processing processes other than the washing process. In addition, the problem is that yellow stain tends to increase during storage of dye images.

SUMMARY OF THE INVENTION Therefore, the first object of the present invention is to provide an image stabilizing solution that allows dye images after processing to be stable for a long period of time and that can suppress the increase in yellow stain in uncolored areas. Second, we provide an image stabilizing solution that allows dye images to remain stable for a long period of time even when the amount of washing water used in the development process is greatly reduced, and that can effectively suppress the increase in yellow stain in uncolored areas. It's about doing. Third, there is virtually no water washing process, and even if the bleach and fixing agents used to remove image silver remain in the image, the dye image remains stable for a long period of time, and the yellow stain remains intact. An object of the present invention is to provide an image stabilizing liquid that can suppress the increase in . Furthermore, fourthly, even if silver whitening agent or fixing agent is mixed in and increases over time,
An object of the present invention is to provide an image stabilizing liquid that does not cause precipitation or mold growth and is stable for a long period of time. Fifthly,
It is an object of the present invention to provide an image stabilizing liquid that is effective in processing not only color light-sensitive materials but also black-and-white light-sensitive materials.

The above object of the present invention is achieved by an image stabilizing solution for processing silver halide photographic materials, which is characterized by containing a water-soluble bismuth compound.

According to a preferred embodiment of the present invention, the following formula.

It contains a water-soluble chelating agent whose stability constant (-1ogKM^) with the water-soluble bismuth compound represented by (T) is 3 or more.

[Here, M represents a bismuth ion, and A represents a complex-forming anion. ]

The present invention will be explained in detail below.

The image stabilizing solution according to the present invention is a processing solution used for image stabilization after color development, marking, fixing, etc., when the photosensitive material to be processed is a silver halide color photographic material. It is used after any processing step, specifically color development or dye-forming processing such as image fixation or bath development bleach-fix processing. Further, in the case of processing black and white photosensitive materials, it is used after forming a silver image. In addition, if the washing process is not performed or if it is used after washing with a very small amount of water, the developer,
It also includes cases where the purpose is also to wash out chemical components such as bleaching agents and fixing agents that have adhered to the photosensitive material or are contained in the photosensitive material before the image stabilization treatment of the present invention. When the treatment with the stabilizing liquid of the present invention is used as a substitute for washing with water, the amount of replenishment of the stabilizing liquid that matches the amount of washing water is the photographic material 1-
The light is supplemented at about 2.5t to 25-25t, preferably 1
t~50-1, more preferably 200rRt~50-1. In this case, washing with a large amount of water other than simple rinsing is not necessary.

The water-soluble bismuth compound used in the image stabilizing solution according to the present invention is one that dissolves in an aqueous solution, such as an oxide, a halide, a nitrate, a sulfate, a carbonate, a hydroxide, or a water-soluble chelate. It may be in any form such as a bismuth complex salt or a complex with an agent. For example, bismuth trioxide,
Bismuth hydroxide, bismuth pentoxide, meta-bismuth salt, ortho-bismuth salt, bismuth chloride, bismuth fluoride, bismuth oxyfluoride, bismuth trifluoride, bismuth pentafluoride, bismuth chloride, bismuth oxychloride, bismuth trichloride, Bismuth chloride, bismuth bromide, bismuth oxybromide, bismuth iodide, bismuth oxyiodide, bismuth hydrogen iodide tR1, hixmuth nitrate, bismuth oxynitrate, bismuth subnitrate, bismuth sulfate, and bismuth carbonate can be used. A bismuth compound formed by forming a bismuth complex with an arsenic compound and a metal ion chelating agent has particularly good water solubility and is preferably used as a water-soluble bismuth compound.In this case, the bismuth compound and the chelating agent are used separately for image stabilization. A complex can be formed by adding it to the liquid, or a complex consisting of a water-soluble bismuth compound and a water-soluble chelating agent can be formed in advance and added.
i□□□″□1ill,”,'II.

The amount of water-soluble bismuth compound used is 1/0.001
It can be used in the range of ~100g; if it is too small, the effect of stabilizing the dye image and preventing the rise of yellow stain will be weak, and if it is too large, precipitation will easily occur due to the formation of excessive insoluble bismuth compounds, resulting in unfavorable results. becomes.

The preferred range of use is 0.01 to 50 g, particularly preferably 0.01 to 20 g.

Among the water-soluble bismuth compounds, those preferably used are bismuth chloride, bismuth nitrate, bismuth sulfate, etc. These are mixed with a water-soluble chelating agent to form a bismuth complex salt or complex before use. is desirable.

The water-soluble chelating agent that can be used in the image stabilizing solution according to the present invention preferably has a chelate stability constant (-1og KMA described above) of 3 or more with bismuth ions. More preferably, -1ag K M A is 8 or more, particularly preferably 20 or more, but these stability constants are
Since the conditions under which the stabilizing liquid is used vary depending on, for example, the hydrogen ion concentration and the amount of other components mixed in, it is generally not possible to select the optimum compound based on the stability constant alone. Therefore, any compound having a stability constant of 3 or more can be used, and it is preferable that the complex has low water solubility and a high chelate stability constant.

Examples of these water-soluble chelating agents include aminopolycarboxylic acid chelates such as diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, diamino-10panoltetraacetic acid, and transcyclohexanediaminetetraacetic acid;
Aminophosphonic acid chelating agents such as ethylenediaminetetrakismethylenephosphonic acid and nitrilotrimethylenephosphonic acid; organic phosphonic acid chelates such as 1-hydroxyethylidene-1,1-diphosphonic acid and 1,1-diphosphonoethane-2-carboxylic acid; agent, 2-phosphonobutane-
Phosphonocarboxylic acid chelating agents such as 1,2,4-tricarboxylic acid, 1-hydroquine-1-phosphonov”lovan-1.2.3-)licarboxylic acid, polycarboxylic acid chelating agents such as salicylic acid and citric acid, catechol-3,
Organic sulfonic acid chelating agents such as 5-disulfonic acid, condensed phosphoric acids such as sodium birophosphate, sodium tetrapolyline powder, and sodium hexametaphosphate can be used. Preferred chelating agents in the present invention include diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid,
Examples include condensed phosphates and their salts.

Particularly preferred chelating agents include 1-hydroxyethylidene-1,1-diphosphonic acid and alkali metal salts, ammonium salts, and ethanolamine salts thereof. Chelating agents that can be used in the present invention are not limited to these. It is also particularly desirable to use two or more chelating agents in combination.

The image stabilizing liquid according to the present invention may contain other compounds. Compounds that can be added include various buffering agents, such as borates, metaborates, borax, phosphates, monocarboxylic acid salts, dicarboxylic acid salts, polycarboxylic acid salts,
Oki1□ dicarboxylate, amino acid, primary phosphate, secondary phosphate, tertiary phosphate, sodium hydroxide, potassium hydroxide, ammonia aqueous solution, various surfactants, fungicides, preservatives, organic sulfur There are compounds etc. In the present invention, compounds that are conventionally known yellow stain improvers, such as altehyde compounds, fluorescent whitening agents, ultraviolet absorbers, etc., may be used in combination.

The pH value of the stabilizing solution according to the present invention is KpH for image preservation.
o, 1~IOK! The preferred range is pH 2 to 9, more preferably pH 3 to 7.

The processing temperature during the stabilization treatment using the image stabilizing liquid according to the present invention is 0°C to 60°C, preferably 20°C to 45°C.
A range of ℃ is good.

Processing using the image stabilizing liquid according to the present invention is carried out using, for example, a stabilizing bath or a stabilizing processing tank, and this processing tank is a multi-stage countercurrent type technology (S, R).

Goldwassar, , 7 Water Flo
rate in immersion-wash
input of motion-picture fil
m”: 1 Jour, SMPTE, , 6f248-253.
May (1955)) is preferable, and the amount of replenishment of the washing water for light supplementation and the image stabilizing solution according to the present invention can be greatly reduced.

The image stabilizing solution according to the present invention can be used in any processing step after forming a dye image by development processing, but especially - image-boundary image bleach-fixing processing, bleaching processing, or bleach-fixing processing. Afterwards, it is desirable to perform a stabilization process using the stabilizing liquid according to the present invention, and after these processes, performing an image stabilization process without substantially washing with water improves image storage stability and prevents yellow stain. The effect is most effectively demonstrated, and the effect is also great in terms of relief. Furthermore, the image stabilizing solution according to the present invention exhibits its maximum effect when an organic acid ferric complex salt is used as the silver bleaching agent. However, the processing using the image stabilizing liquid according to the present invention is not limited to these specific processing forms, and any processing form can exhibit an effect superior to conventional image stabilizing effects. I can do it.

The organic acid ferric complex salt as a silver bleaching agent, which exhibits the greatest effect when combined with the treatment with the stabilizing solution according to the present invention, is used in bleaching solutions, bleach-fixing solutions, etc. It has the effect of oxidizing metallic silver and converting it into silver halide, and at the same time coloring the uncolored part of the coloring agent. Its structure is an organic acid such as aminopolycarboxylic acid or polycarboxylic acid such as oxalic acid or citric acid. , coordinated with metal ions. The most preferred organic acid used to form such an organic acid ferric complex salt is, for example, a polycarboxylic acid or an amine polycarboxylic acid represented by the following general formula [rl or Ell].

General formula (T) HOCO-AI Z -A'2- C00H General formula [
11] [In each general formula, Al, A2. A3, A4, A5
and A6 each represent a substituted or unsubstituted hydrocarbon group, and 2 represents a hydrocarbon group or >N-AI (AI is a hydrocarbon group or a lower aliphatic carboxylic acid).

] These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts, or water-soluble amine salts. The above general formula [■] or [lI]
Typical examples of the aminopolycarboxylic acid or polycarboxylic acid represented by are shown below.

(1) Ethylenediaminetetraacetic acid (2) Diethylenetriaminepentaacetic acid (3) Ethylenediamine-N-(β-oxyethyl) -N,N',N'-triacetic acid Propylenediaminetetraacetic acid (4) Nitrilotriacetic acid (5) Cyclohexanediaminetetraacetic acid Acetic acid (6)
Iminodiacetic acid (7) Dihydroxyethylglycine (8) Ethyl ether diamine tetraacetic acid (9)
Glycol ether diamine tetraacetic acid (10)
xfv:y07 i 7f h la'':, 7..1
Oh,.

(11) Phenylenediaminetetraacetic acid (12) Ethylenediaminetetraacetic acid disodium salt (13) Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt (14) Ethylenediaminetetraacetic acid tetrasodium salt (15) Diethylenetriaminepentaacetic acid pentasodium salt (16) Ethylenediamine -N-(β-oxyethyl)
-N,N',N'-Triacetic acid sodium salt (17) Propylene diamine tetraacetic acid sodium salt (18) Nitrilotriacetic acid sodium salt (19) Cyclohexanediamine tetraacetic acid sodium salt (20) Citric acid (21) Oxalic acid (22) Maleic acid (23) Tartaric acid (24) Succinic acid (25) Sulfamic acid (26) Phthalic acid □ (27) Gluconic acid: Particularly preferred organic acids include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and glycol etherdiaminetetraacetic acid. can give. Even when the organic acid is used in a stabilizing solution, it has a high ability to form a complex with bismuth ions, so it can be used desirably. Particularly desirable results can be obtained when used in combination with a phosphonic acid chelating agent.

In the present invention, silver bleaching agents other than organic acid secondary metal complex salts can be used, and any oxidizing agent can be used, but in particular, persulfates, hydrogen peroxide, iron chloride, ferricyanide, etc. Iron salts can be used suitably.

Furthermore, in the present invention, when using a fixing solution, a bleach-fixing solution, and an image bleaching-fixing solution containing thiosulfate or thiocyanate as the main components, it is extremely effective, but it removes other fixing agents. isn't it. Such a fixing agent makes bleached silver soluble in water as a soluble silver complex salt, and examples of the fixing agent include sodium thiosulfate, ammonium thiosulfate, potassium thiosulfate, potassium thiocyanate, ammonium thiocyanate, and sodium thiocyanate. etc. can be cited as representative examples.

It is possible to omit the water rinsing treatment after the stabilization treatment using the stabilizing liquid according to the present invention, but in this case, rinsing with a small amount of water within a very short time, surface cleaning, etc. may be optionally performed as necessary. You can also do it. It is also effective to perform this small amount of water washing by contacting with a sponge or the like containing water.

The processing method using a stabilizing liquid according to the present invention is suitable for silver halide color photographic materials such as color paper, reversal color paper, color positive film, color negative film, color reversal film, color X-ray film, etc. It can also be used to process photosensitive materials.

In addition, when the stabilizing liquid according to the present invention contains a soluble silver salt, silver can also be recovered from the liquid. As a silver recovery method, ion exchange resin method, metal substitution method, electrolysis method, silver sulfide precipitation method, etc. can be used.

Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples.

Example-1 Sakura Shimo-paper was partially exposed to light to give a reflection density of 1.5, and after normal color development, bleach-fixing, and washing with water, the formulation area shown in Table 1 below was prepared. Nos. 1 to 14 were immersed in a solution of the finishing recipe at 33° C. for 1 minute, and then dried to obtain a sample.

The red reflection density and the yellow stain density of the unexposed area were measured, and the sample after measurement was placed in a constant temperature and humidity bath at 60° C. and 80% RH for 20 days to deteriorate the image strength. The density of this sample was again measured, and the red reflectance reduction rate and yellow stain density were measured, and the results are shown in Table 2.

As is clear from Table 2 in the margin below, compared to the stabilizing solution 1@1, which simply adjusted the pH value, the comparative examples (m2 to ug5) showed almost no reduction in yellow stain. It can be seen that when the occurrence is small, the red reflection density is significantly lowered, which is not desirable. On the other hand, the image stabilization processing according to the present invention (l@6~Na
In No. 14), the rate of decrease in red reflection density is extremely small, the degree of occurrence of yellow stain is also very small, and the dye image and unexposed areas are also stably maintained.

Example-2 Sakura Power Paper (roll form) [Konishi Roku Photo Industry ■
After the photoprinting process was carried out, continuous light supplementation processing (hereinafter referred to as running processing) was carried out using an automatic developing machine (endless belt conveyance type) according to the following experiment. The treatment steps and composition of the treatment liquid at this time are as follows.

[Standard treatment process]

1. Color development 33℃ 3 minutes 30 seconds 2. Standard fixation 33℃ 1 minute 30 seconds 3. Stabilization treatment
25℃~30℃ 3 minutes 4, drying 75℃~80℃
The composition of the treatment solution used for about 2 minutes was as follows.

[Color development tank liquid]

[Color developer replenisher] [Heading Fixer Tank Fluid].

□l□ [Bleach-fixing auxiliary solution A] [Bleach-fixing solution auxiliary amount B] Fill an automatic processor with the above color developing tank solution, bleach-fixing tank solution, and the following stabilizing solution, and heat for 3 minutes while processing color paper. A running test was conducted at intervals while supplementing the color developer replenisher, bleach-fixing supplements A and B, and stable supplement solution through a metering cup. The amount of replenishment was 324 rR1 for the color development tank for color vapor knee, and 25 for each of the bleach-fixing auxiliary solutions A and B for the bleach-fixing tank. The stabilization bath is divided into three tanks (11th, 2nd,
a third stabilizing bath), a stabilizing liquid flows into the third stabilizing bath, the overflow from the third stabilizing bath enters the second stabilizing bath, the overflow from the second stabilizing bath enters the first stabilizing bath; A type of overflow from the stable bathtub to the outside of the processing machine (counter current method) is used to perform the process.

The convergence of the running process is that in Experiment 1, the total amount of bleach-fixing solution supplementing to the bleach-fixing bath (replenisher A, supplementary solution B, and amount of color developing solution that adheres to and enters the photosensitive material) was twice the tank capacity. Tagi was defined as the time when convergence was reached.

Experiment - ■ The first to third stable bath tank liquids and their auxiliary liquids were prepared by diluting an aqueous solution containing 2 g of glacial acetic acid per 1 z with sodium hydroxide.
Color paper 1n using V@ adjusted solution for H4,2
? Running processing was performed using the 200- light supplement. When the solution composition and components mixed in the bleach-fix solution reach convergence, each tank solution is collected, and ml-9 of each formulation in Table 3 is added to each tank solution in the first, second, and third stabilizing baths. Add the compound shown and further hydroxylate) Adjust the pH value to 4.0 with an aqueous IJ solution.
Each was adjusted to 2.

Using the reporter tank solution in the first to third stabilizing baths, the cherry paper was partially exposed to light to give a reflection density of 1.5, and then developed, and the red reflection density and the unexposed area were measured. Yellow stain concentration was measured. 60% of the sample after measurement
The image was placed in a constant humidity tank at 80% RH for 10 days to deteriorate the image strength. Measure the concentration of the sample again after storage,
Measure red reflection density reduction rate and yellow stain density,
The results are shown in Table 4. For comparison, Table 4 also shows the results of samples in which the stabilizing solution was washed with water (a process that requires a large amount of washing water, which is generally performed at present).

Experiment-2 After the running treatment of Experiment-1, the stabilizing solution in the third stabilizing bath (containing each compound in Table 3) was filled into a 500-mL Erlenmeyer flask and left at room temperature, and the precipitate was added at an interval of IO days. Table 5 shows the results of the observations.

Margin below Table 5 -: Transparent, no precipitate.

12. A small amount of precipitate is generated, and the liquid becomes slightly cloudy.

Sweet: A large amount of precipitate occurs, and the liquid becomes completely cloudy.

As is clear from Table 4 above, compared to the standard water washing process, yellow stain increased when the water washing process was removed and the stabilization process was performed directly with a stabilizing solution whose pH was adjusted with acetic acid. It can be seen that the color fading is slightly large and the fading of the pigment is also relatively large. Although not described here, when the pH was not adjusted, the yellow stain was 0.3 or higher. Next, we used conventional yellow stain prevention technologies such as citric acid (polycarboxylic acid), potassium aluminum sulfate ditetrahydrate (water-soluble aluminum salt), and zinc sulfate (
Stabilizing treatment using either water-soluble bendic acid) or zirconium sulfate (water-soluble zirconium salt) alone or in combination can only slightly prevent the occurrence of yellow stain, and stabilizing solutions containing formaldehyde (aldehyde compound) During processing, the density of cyan dye decreases! It can also be seen that it is promoted and cannot be put to practical use.

However, it can be seen that the stabilizing solution treatment according to the present invention is extremely effective in preventing a significant increase in yellow stain without causing a decrease in the concentration of cyan dye.

Furthermore, as is clear from Table 5, the present invention completely prevents the occurrence of precipitation due to storage of the stabilizing liquid over time, and also prevents the liquid from spoiling and the growth of mold and bacteria. It can be seen that it is extremely effective in reducing the number of children, and that it is possible to reduce the amount of water used for washing.

Example-3 After developing black and white paper Yoshino Fs (manufactured by Konishiroku Photo Industries Co., Ltd.) using the developer Conitone (manufactured by Konishiroku Photo Industries Co., Ltd.), the fixer Conifix (manufactured by Konishiroku Photo Industries Co., Ltd.) was used. The sample was fixed using a 100% water solution, washed with running water for 2 minutes, and then immersed in a stabilizing solution shown in Table 6 at 20° C. for 1 minute and dried.

Each sample obtained by processing the margins was heated to 60°C, humidity 80%, and illuminance 2.
Strength deterioration was performed for 40 days under illumination light of 0.00 lux. As a result, the minimum white density (stin) of the unexposed area of the sample of the present invention is significantly lower than that of the comparative sample, and the silver image area of the sample of the present invention turns brown, whereas the comparative sample turns brown. The degree of discoloration was significantly lower.

Furthermore, if the stabilizing solution was used directly after fixing without washing with water, this difference would be even more significant, whereas the comparative stabilizing solution would cause an increase in yellow stain in unexposed areas and browning in silver image areas. However, in the stabilizing solution of the present invention, both the increase in staining in the unexposed area and the browning in the silver image area were significantly suppressed. This shows that the present invention is also effective for black and white photosensitive materials.

Patent applicant: Konishi University Photo Industry Co., Ltd. 35-

Claims (2)

[Claims] (1) An image stabilizing solution for processing silver halide photographic materials, which is characterized by containing a water-soluble bismuth compound. (2) Claim 1 characterized by containing a water-soluble chelate compound having a stability constant (-tag K, MA) of 3 or more with the water-soluble bismuth compound represented by the following formula [I]. An image stabilizing liquid for processing silver halide photographic light-sensitive materials as described in 2. Formula [■] [Here, M represents a bismuth ion, and A represents a complex-forming anion. ]